US5021593A - Ruthenium-optically active phosphine complex - Google Patents
Ruthenium-optically active phosphine complex Download PDFInfo
- Publication number
- US5021593A US5021593A US07/551,110 US55111090A US5021593A US 5021593 A US5021593 A US 5021593A US 55111090 A US55111090 A US 55111090A US 5021593 A US5021593 A US 5021593A
- Authority
- US
- United States
- Prior art keywords
- bichep
- optically active
- ruthenium
- phosphine complex
- sub
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 5
- SKCMIKXIHUVXEG-UHFFFAOYSA-N dicyclohexyl-[2-(2-dicyclohexylphosphanyl-6-methylphenyl)-3-methylphenyl]phosphane Chemical group CC=1C=CC=C(P(C2CCCCC2)C2CCCCC2)C=1C=1C(C)=CC=CC=1P(C1CCCCC1)C1CCCCC1 SKCMIKXIHUVXEG-UHFFFAOYSA-N 0.000 claims abstract description 4
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 230000003287 optical effect Effects 0.000 abstract description 15
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006317 isomerization reaction Methods 0.000 abstract description 4
- 238000006884 silylation reaction Methods 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 239000013078 crystal Substances 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 29
- 239000002904 solvent Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- VWGWKZKGMNQBIK-UHFFFAOYSA-N n-(2-methyl-6-nitrophenyl)acetamide Chemical compound CC(=O)NC1=C(C)C=CC=C1[N+]([O-])=O VWGWKZKGMNQBIK-UHFFFAOYSA-N 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- FCMRHMPITHLLLA-UHFFFAOYSA-N 2-methyl-6-nitroaniline Chemical compound CC1=CC=CC([N+]([O-])=O)=C1N FCMRHMPITHLLLA-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 9
- AKYPSJARSQSCHJ-UHFFFAOYSA-N 2-iodo-1-methyl-3-nitrobenzene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1I AKYPSJARSQSCHJ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- UMVWSQDHHCCZCJ-UHFFFAOYSA-N 1-dicyclohexylphosphoryl-2-(2-dicyclohexylphosphoryl-6-methylphenyl)-3-methylbenzene Chemical group CC1=CC=CC(P(=O)(C2CCCCC2)C2CCCCC2)=C1C1=C(C)C=CC=C1P(=O)(C1CCCCC1)C1CCCCC1 UMVWSQDHHCCZCJ-UHFFFAOYSA-N 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- KJPBHWPECBAAAA-UHFFFAOYSA-N 1-bromo-2-(2-bromo-6-methylphenyl)-3-methylbenzene Chemical group CC1=CC=CC(Br)=C1C1=C(C)C=CC=C1Br KJPBHWPECBAAAA-UHFFFAOYSA-N 0.000 description 4
- UFWJYJCNLOWJCO-UHFFFAOYSA-N 1-methyl-2-(2-methyl-6-nitrophenyl)-3-nitrobenzene Chemical group CC1=CC=CC([N+]([O-])=O)=C1C1=C(C)C=CC=C1[N+]([O-])=O UFWJYJCNLOWJCO-UHFFFAOYSA-N 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910003944 H3 PO4 Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- HKYSIUYOULVHTO-UHFFFAOYSA-N [chloro(cyclohexyl)phosphoryl]cyclohexane Chemical compound C1CCCCC1P(=O)(Cl)C1CCCCC1 HKYSIUYOULVHTO-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 phosphine compound Chemical group 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 4
- MCUUKQCKNKUMBP-UHFFFAOYSA-N 2-(2-amino-6-methylphenyl)-3-methylaniline Chemical group CC1=CC=CC(N)=C1C1=C(C)C=CC=C1N MCUUKQCKNKUMBP-UHFFFAOYSA-N 0.000 description 3
- JZEOVPGWIWSSAK-UHFFFAOYSA-N N1-(2-methyl-4-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C([N+]([O-])=O)C=C1C JZEOVPGWIWSSAK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000011914 asymmetric synthesis Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- YONLFQNRGZXBBF-ZIAGYGMSSA-N (2r,3r)-2,3-dibenzoyloxybutanedioic acid Chemical compound O([C@@H](C(=O)O)[C@@H](OC(=O)C=1C=CC=CC=1)C(O)=O)C(=O)C1=CC=CC=C1 YONLFQNRGZXBBF-ZIAGYGMSSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical group C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- PMVKSDPWGBZTFB-XFXZXTDPSA-N ethyl (z)-2-acetamido-3-phenylprop-2-enoate Chemical compound CCOC(=O)C(\NC(C)=O)=C\C1=CC=CC=C1 PMVKSDPWGBZTFB-XFXZXTDPSA-N 0.000 description 2
- YIVZYFDBEPMPNL-UHFFFAOYSA-N ethyl 2-acetamido-3-phenylpropanoate Chemical compound CCOC(=O)C(NC(C)=O)CC1=CC=CC=C1 YIVZYFDBEPMPNL-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- XZNZIRYSCNVXJU-UHFFFAOYSA-N 1-dicyclohexylphosphoryl-3-methyl-2-(2-methylphenyl)benzene Chemical group CC1=CC=CC=C1C1=C(C)C=CC=C1P(=O)(C1CCCCC1)C1CCCCC1 XZNZIRYSCNVXJU-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BPEXTIMJLDWDTL-UHFFFAOYSA-N 2`-Methylacetanilide Chemical compound CC(=O)NC1=CC=CC=C1C BPEXTIMJLDWDTL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- WHLQQRGHOPIIMQ-UHFFFAOYSA-N [2-(2-diphenylphosphanyl-6-methylphenyl)-3-methylphenyl]-diphenylphosphane Chemical group CC=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1C=1C(C)=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 WHLQQRGHOPIIMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000002668 chloroacetyl group Chemical group ClCC(=O)* 0.000 description 1
- SKCNIGRBPJIUBQ-UHFFFAOYSA-N chloroform;ethyl acetate Chemical compound ClC(Cl)Cl.CCOC(C)=O SKCNIGRBPJIUBQ-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- MFUREGQXOWBFEN-UHFFFAOYSA-L dicyclohexyl-[2-(2-dicyclohexylphosphanyl-6-methylphenyl)-3-methylphenyl]phosphane ruthenium(2+) diacetate Chemical compound [Ru+2].CC([O-])=O.CC([O-])=O.CC=1C=CC=C(P(C2CCCCC2)C2CCCCC2)C=1C=1C(C)=CC=CC=1P(C1CCCCC1)C1CCCCC1 MFUREGQXOWBFEN-UHFFFAOYSA-L 0.000 description 1
- PLWIPBDGSJUQFK-UHFFFAOYSA-L dicyclohexyl-[2-(2-dicyclohexylphosphanyl-6-methylphenyl)-3-methylphenyl]phosphane;iodoruthenium(1+);1-methyl-4-propan-2-ylbenzene;iodide Chemical compound I[Ru]I.CC(C)C1=CC=C(C)C=C1.CC=1C=CC=C(P(C2CCCCC2)C2CCCCC2)C=1C=1C(C)=CC=CC=1P(C1CCCCC1)C1CCCCC1 PLWIPBDGSJUQFK-UHFFFAOYSA-L 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000011982 enantioselective catalyst Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ALMHSXDYCFOZQD-UHFFFAOYSA-N n-(3-methylphenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(C)=C1 ALMHSXDYCFOZQD-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical class [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
Definitions
- This invention relates to a ruthenium-optically active phosphine complex which is useful as a catalyst for various organic syntheses, particularly asymmetric hydrogenation, asymmetric isomerization, and asymmetric silylation.
- BINAP 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl
- JP-A the term "JP-A” as used herein means an "unexamined published Japanese patent application”
- BIPHENP 2,2'-bis(diphenylphosphino)-6,6'-dimethyl-1,1'-biphenyl
- optically active carboxylic acids include a process comprising chemically oxidizing a naturally occurring optically active alcohol or aldehyde to obtain a corresponding carboxylic acid, a process comprising optically resolving a racemic carboxylic acid with an optically active amine, and a process comprising converting a racemic carboxylic acid to its ester and partially hydrolyzing the ester with the aid of an enzyme or a microorganism to obtain a desired carboxylic acid.
- an optically active carboxylic acid can be obtained by asymmetric hydrogenation of an ⁇ , ⁇ -unsaturated carboxylic acid in the presence of a chiral catalyst.
- a chiral catalyst In this case, satisfactory results may be obtained in the syntheses of some carboxylic acids but, in general, the choice of an optically active phosphine as a component of the chiral catalyst is of importance, and there have been developed only few chiral phosphine compounds that are applicable for general purposes.
- An object of this invention is to provide a rutheniumoptically active phosphine complex having BICHEP as a ligand, which is useful as a catalyst having markedly improve catalytic activity in selectivity, durability, and the like irrespective of the reaction mode and the reaction substrate.
- BICHEP which is used as a ligand of the complex of the present invention can be synthesized by, e.g., the process reported in Miyashita, et al., The 58th Springtime Annual Meeting of The Chemical Society of Japan, Lecture Preprint II, pp. 1492 (1989).
- o-toluidine (2) is treated with acetic anhydride to acetylate the amino grou to obtain N-acetyl-o-toluidine (3).
- the compound (3) is nitrated with nitric acid to obtain 2-acetylamino-3-nitrotoluene (4) which is then hydrolyzed with a hydrochloric acid aqueous solution to obtain 2-amino-3-nitrotoluene (5).
- the compound (5) is diazotized with sodium nitrite in the presence of sulfuric acid and then treated with an aqueous potassium iodide to obtain crude 2-iodo-3-nitrotoluene (6).
- the crude product is recrystallized from ethanol to obtain a pale yellow pure compound (6)
- the compound (6) is allowed to react with stirring at 200° C. for 10 hours in the presence of a copper powder, and the reaction mixture is extracted with benzene using a Soxhlet extractor to obtain 6,6'-dimethyl-2,2'-dinitro-1,1'-biphenyl (7).
- the compound (7) is hydrogenated in the presence of a Raney nickel W2 type catalyst using hydrazine hydrate as a hydrogen source to obtain crude 6,6'-dimethyl-2,2'-diamino-1,1'-biphenyl (8). After the catalyst is removed, the solvent is removed under reduced pressure to obtain a pale yellow pure compound (8).
- the compound (8) is dissolved in a 47% hydrobromic acid aqueous solution, and a sodium nitrite aqueous solution is slowly added dropwise thereto under ice-cooling (0° C.), followed by stirring at -5° to -3° C. for 2.5 hours.
- the resulting solution is added slowly to a separately prepared refluxing solution of cuprous bromide in a 47% hydrobromic acid aqueous solution.
- the mixture is further heated at reflux for 2.5 hours.
- To the reaction mixture are added methylene chloride and water, the mixture is stirred, and an organic layer is concentrated to obtain a black crude crystal.
- the crystal is purified twice by means of column chromatography to obtain 6,6'-dimethyl-2,2'-dibromo-1,1'-biphenyl (9) as a white crystal.
- the compound (9) is dissolved in tetrahydrofuran, the solution is cooled to -78° C., and a hexane solution of t-butyllithium is slowly added dropwise to the cooled solution. After the addition, the temperature is elevated to - 45° C., and the reaction is continued for an additional 4 hours.
- the racemic compound (11) is dissolved in a mixed solvent of ethyl acetate and chloroform under heating, and a hot ethyl acetate solution of (-)-dibenzoyltartaric acid is added thereto, followed by allowing to stand to precipitate.
- the precipitated crystal is repeatedly recrystallized until the crystal shows a constant optical rotation
- the purified crYstal is suspended in toluene, and a 2N sodium hydroxide aqueous solution is added thereto to convert the compound to a free diphosphine oxide (12). Recrystallization from chloroform-ethyl acetate gives pure 2,2'-bis(dicyclohexylphosphinyl)-6,6'-dimethyl-1,1'-biphenyl (12).
- Xylene and triethylamine are added to the optically pure 2,2'-bis(dicyclohexylphosphinyl)-6,6'-dimethyl-1,1'biphenyl (12) ([ ⁇ ] D 20 :-75.3° ), and trichlorosilane is added thereto under ice-cooling.
- the mixture is heated at 120° C. for 2 hours and then at 130° C. for 2 hours, followed by cooling to room temperature.
- a 30% sodium hydroxide aqueous solution is added thereto to completely dissolve any solid matter, methylene chloride is added, and the mixture is refluxed at 60° C. for 2 hours.
- An organic layer is separated and dried, and the solvent is removed by distillation. The residue is recrystallized from methanol to obtain a white crystal of BICHEP.
- the ruthenium-optically active phosphine complex of the present invention is a ruthenium complex having BICHEP as a ligand and is represented by either one of the following formulae (II), (III), or (IV):
- R 0 represents a lower alkyl group (preferably containing from 1 to 4 carbon atoms) or a substituted or unsubstituted aryl group (e.g., a phenyl group),
- X and X' simultaneously represent the same halogen atom (e.g., an idodine atom, a chlorine atom, a bromine atom); and A represents a substituted or unsubstituted phenyl group, or
- R 00 represents a tertiary amine (preferably having lower alkyl groups each containing from 1 to 4 carbon atoms).
- the complex of formula (II) can be prepared according to the process disclosed in U.S. Pat. No. 4,739,084; the complex of formula (III) can be prepared according to the process disclosed in European Patent 366,390A; and the complex of formula (IV) can be prepared according to the process disclosed in U.S. Pat. No. 4,691,037, respectively.
- R represents a hydrogen atom or a lower alkyl group (preferably containing from 1 to 4 carbon atoms)
- R 1 represents a lower alkyl group (preferably containing from 1 to 4 carbon
- the catalyst of the present invention is used in an amount of from 0.02 to 0.0001 mole, preferably from 0.01 to 0.001 mole, per mole of the ⁇ , ⁇ -unsaturated carboxylic acid.
- solvents can be used.
- suitable solvents are alcohols (e.g., methanol, ethanol, and isopropanol), tetrahydrofuran, benzene, toluene, etc., and mixtures thereof.
- the solvent is used in an amount of from 0.5 to 20 l per mole of the ⁇ , ⁇ -unsaturated carboxylic acid.
- the hydrogen pressure for reaction usually ranges from 1 to 100 kg/cm 2
- the reaction temperature is from 5° to 70° C., and preferably from 10° to 30° C.
- the reaction is continued until the pressure is diminished to a prescribed level, and the reaction time usually ranges from 10 minutes to 20 hours, though depending on the reaction time.
- the solvent is removed by distillation, and the residue is neutralized.
- the catalyst is then removed by extraction with chloroform, carbon tetrachloride, dichloromethane, etc.
- the residue is again rendered acidic with a mineral acid and then extracted with diethyl ether, chloroform, dichloromethane, benzene, toluene, ethyl acetate, etc. to obtain a desired optically active carboxylic acid or an ester thereof.
- the reaction mixture was poured into 3 l of ice-water, and 1 l of an aqueous 53% potassium iodide was added thereto. After stirring at 80° C. for 10 hours, the reaction mixture was treated with 100 g of sodium hydrogensulfite. A supernatant was removed, and insoluble matters were extracted thrice with 500 ml of dichloromethane. An organic layer was neutralized and washed with a saturated sodium hydrogencarbonate aqueous solution, washed with distilled water, and then dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure to obtain a yellowish brown crude crystal.
- a suspension of 3 ml of a Raney nickel W2 type catalyst in ethanol was slowly added thereto by means of a syringe while maintaining the activity. Thereafter, the mixture was heated at reflux in an oil bath until the whole of the hydrazine was consumed.
- the solution was slowly added to a refluxing solution of 73.7 mg (5 mmole) of cuprous bromide in 1.5 ml (13 mmole) of 47% hydrobromic acid, and the mixture was refluxed for 2.5 hours.
- To the reaction mixture were added 30 ml of dichloromethane and 20 ml of distilled water to thereby thoroughly extract an organic layer.
- the extract was washed successively with 10 ml of a saturated sodium hydrogencarbonate aqueous solution, 10 ml of distilled water, and 10 ml of a saturated potassium nitrate aqueous solution and dried over anhydrous sodium sulfate.
- Purification may be accomplished through one column chromatography by controlling the column volume, the solvent concentration, and the like.
- the mixture was gradually warmed and allowed to react for at least 4 hours while maintaining the temperature at about -45° C.
- the mixture was again cooled to -78° C., and 5.50 g (22.2 mmole) of dicyclohexylphosphinic chloride (10) thoroughly dissolved in 20 ml of dry tetrahydrofuran was added dropwise thereto, followed by stirring overnight. During the stirring, the temperature was allowed to elevate with a Dewar vessel being fixed. After the reaction was continued until the mixture was warmed to room temperature by spontaneous temperature elevation, the mixture was heated at reflux for 3 hours. The solvent was removed by distillation under reduced pressure, and the residue was completely dissolved in 20 ml of toluene. A white insoluble matter thus formed was removed by filtration.
- the resulting toluene solution was washed successively twice with distilled water, thrice with a 2N sodium hydroxide aqueous solution, and once with distilled water. An adequate amount of potassium carbonate was added thereto for drying. The potassium carbonate was separated by filtration through a cotton plug, and the solvent was removed by distillation under reduced pressure. To the residue was added about 10 ml of acetone, and the solution was sufficiently stirred while lightly warming with a drier. A thus precipitated white crystal was collected by filtration to obtain the novel compound of the present invention, 2,2'-bis(dicyclohexylphosphinyl)-6,6'-dimethyl-1,1'-biphenyl (11) and a 39.3% yield.
- Optical rotations of both of a sparingly soluble diastereomer (salt of opposite signs, i.e., (+)(-)-salt) and an easily soluble diastereomer (salt of same signs, i.e., (-)(-)-salt) were measured. If the measured optical rotations were not appreciably different from the values shown below, the product was neutralized as follows to obtain an optically active diphosphine oxide. The crystal was thoroughly dissolved in about 40 ml of a 2N sodium hydroxide aqueous solution and about 40 ml of toluene with stirring, followed by liquid-liquid separation. The sodium hydroxide layer was extracted twice or thrice with about 20 ml of toluene.
- the resulting optically active compound (12) was repeatedly recrystallized using ethyl acetate and chloroform until the specific rotatory power of the crystal was no more varied.
- the container was then allowed to cool to room temperature, and 0.43 ml (4.17 mmole) of trichlorosilane was injected therein using a previously ice-cooled syringe.
- a Schlenk tube containing trichlorosilane to be added had to be kept under ice-cooling. After injection, the content was sufficiently stirred and cooled in an ice bath for several minutes. Upon addition of 0.52 ml (3.73 mmole) of triethylamine, the solution turned yellow and began to solidify. The mixture was again stirred to form a uniform gel. The gel was further allowed to react in an oil bath at 120° C. for 4 hours and then at 130° C. for 2 hours. After allowing to cool to room temperature, several milliliters of xylene was added thereto in a nitrogen atmosphere, and the content was transferred to a Schlenk's tube in a nitrogen atmosphere by using a simplified gloved box.
- the thus obtained optically active BICHEP was repeatedly recrystallized to preferentially crystallize a one-sided enantiomer to increase its optical purity.
- the recrystallization operation was repeated until the specific rotatory power of the crystal no more changed.
- the specific rotatory power of the resulting crystal was taken as a specific rotatory power of an enantiomer of BICHEP having a optical purity of 100%.
- the procedure taken here was as follows.
- the (+)-enantiomer of the optically active diphosphine oxide (12) obtained by reduction was charged in a Schlenk tube equipped with a stirrer in a nitrogen atmosphere. Warm ethyl acetate which had been displaced with nitrogen was added thereto in small portions as a solvent with stirring. At the point when all the solid matter dissolved, the stirring was ceased, and the solution was allowed to cool to room temperature and then cooled in a refrigerator (-3° C.) for about 30 minutes, whereby a semi-transparent crystal of BICHEP was obtained. The solvent was removed by using a syringe in a nitrogen atmosphere, and the crystal was distilled in vacuo to remove any residual solvent and then dried. Specific rotatory power of the resulting crystal was measured with a polarimeter using methylene chloride as a solvent.
- the specific rotatory power of this optically active compound having an optical purity of 100% was found to be +119.7° or -119.7° (the decimal fraction was within the error of the polarimeter).
- the ruthenium-optically active phosphine complex according to the present invention can catalyze asymmetric syntheses, such as asymmetric hydrogenation, asymmetric isomerization, and asymmetric silylation, exhibiting excellent catalytic activity and providing high optical purity.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1-177257 | 1989-07-11 | ||
JP17725789 | 1989-07-11 | ||
JP2-58791 | 1990-03-09 | ||
JP5879190 | 1990-03-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
US5021593A true US5021593A (en) | 1991-06-04 |
Family
ID=26399797
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/551,107 Expired - Fee Related US5087728A (en) | 1989-07-11 | 1990-07-11 | Process for producing carboxylic acids and esters thereof |
US07/551,110 Expired - Lifetime US5021593A (en) | 1989-07-11 | 1990-07-11 | Ruthenium-optically active phosphine complex |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/551,107 Expired - Fee Related US5087728A (en) | 1989-07-11 | 1990-07-11 | Process for producing carboxylic acids and esters thereof |
Country Status (4)
Country | Link |
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US (2) | US5087728A (de) |
EP (2) | EP0408338B1 (de) |
JP (1) | JPH0692427B2 (de) |
DE (2) | DE69025003T2 (de) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5306834A (en) * | 1992-07-16 | 1994-04-26 | Takasago International Corporation | Process for preparing optically active 4-methyl-2-oxetanone |
US5324850A (en) * | 1989-08-23 | 1994-06-28 | Societe Nationale Elf Aquitaine | Preparation of chiral catalysts based on ruthenium and phosphorus complexes |
US5412109A (en) * | 1992-07-16 | 1995-05-02 | Takasago International Corporation | Process for preparing optically active 4-methyl-2-oxetanone |
US5430191A (en) * | 1992-01-31 | 1995-07-04 | Hoffmann-La Roche Inc. | Phosphorus compounds |
US5508438A (en) * | 1992-01-31 | 1996-04-16 | Hoffmann-La Roche Inc. | Phosphorus compounds |
US5530162A (en) * | 1992-04-13 | 1996-06-25 | Research Corporation Technologies, Inc. | Process for the hydrogenation of aryl phosphines and products obtained therefrom |
US5808162A (en) * | 1995-07-21 | 1998-09-15 | Takasago International Corporation | Chiral unsymmetric diphosphine compound and transition metal complex containing the same as ligand |
US20030093387A1 (en) * | 2000-06-09 | 2003-05-15 | Brett Nakfoor | Electronic ticketing system and method |
US20050021365A1 (en) * | 2000-06-09 | 2005-01-27 | Nakfoor Brett A. | Multi-input access device and method of using the same |
US20050021364A1 (en) * | 2000-06-09 | 2005-01-27 | Nakfoor Brett A. | Method and system for access verification within a venue |
US20060095344A1 (en) * | 2000-06-09 | 2006-05-04 | Nakfoor Brett A | System and method for fan lifecycle management |
WO2007082026A2 (en) * | 2006-01-10 | 2007-07-19 | The Trustees Of Boston College | Catalytic enantioselective silylations of substrates |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5334758A (en) * | 1989-07-05 | 1994-08-02 | Takasago International Corporation | Process for preparing optically active carboxylic acid |
US5344970A (en) * | 1990-12-10 | 1994-09-06 | Albemarle Corporation | Hydrogenation of aromatic-substituted olefins using organometallic catalyst |
EP0570764B1 (de) * | 1992-05-18 | 2001-07-18 | F.Hoffmann-La Roche & Co. Aktiengesellschaft | Asymmetrische Hydrierung |
JPH06263777A (ja) * | 1993-03-12 | 1994-09-20 | Takasago Internatl Corp | ホスフィン化合物およびこれを配位子とする遷移金属−ホスフィン錯体 |
EP0634410B1 (de) * | 1993-07-15 | 1997-02-26 | F. Hoffmann-La Roche Ag | Verfahren zur Herstellung eines N-tert.Butylisochinolin-3-carboxamid Derivates und Zwischenprodukte in diesem Verfahren |
ATE177427T1 (de) * | 1993-10-08 | 1999-03-15 | Hoffmann La Roche | Optisch aktive phosphorverbindungen |
US5935892A (en) | 1994-02-22 | 1999-08-10 | California Institute Of Technology | Supported phase catalyst |
WO2004031110A2 (de) * | 2002-10-01 | 2004-04-15 | Dieter Arlt | Isomerisierung von chiral einheitlichen o,o'-dihydroxy-biphenylderivaten |
WO2005051882A1 (en) * | 2003-11-27 | 2005-06-09 | Takasago International Corporation | Process for producing optically active 3-(4-hydroxyphenyl)propionic acids |
AT501193B1 (de) * | 2004-12-27 | 2007-03-15 | Dsm Fine Chem Austria Gmbh | Verfahen zur übergangsmetall - katalysierten asymmetrischen hydrierung von acrylsäurederivaten |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4400548A (en) * | 1981-08-17 | 1983-08-23 | Union Carbide Corporation | Hydroformylation process using bisphosphine monooxide ligands |
US4748261A (en) * | 1985-09-05 | 1988-05-31 | Union Carbide Corporation | Bis-phosphite compounds |
US4904808A (en) * | 1986-06-13 | 1990-02-27 | Eastman Kodak Company | Chelate ligands for low pressure hydroformylation catalyst and process employing same |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6061587A (ja) * | 1983-09-16 | 1985-04-09 | Takasago Corp | ロジウム−ホスフイン錯体 |
EP0272787B1 (de) * | 1986-11-14 | 1992-05-06 | Takasago International Corporation | Katalytische Produktion von optisch aktiven Carbonsäuren |
DK168069B1 (da) * | 1987-11-11 | 1994-01-31 | Hoffmann La Roche | Isoquinolinderivater og en fremgangsmaade til fremstilling af octahydroisoquinoliner ud fra derivaterne |
-
1990
- 1990-07-07 JP JP2178519A patent/JPH0692427B2/ja not_active Expired - Fee Related
- 1990-07-11 US US07/551,107 patent/US5087728A/en not_active Expired - Fee Related
- 1990-07-11 DE DE69025003T patent/DE69025003T2/de not_active Expired - Fee Related
- 1990-07-11 US US07/551,110 patent/US5021593A/en not_active Expired - Lifetime
- 1990-07-11 EP EP90307583A patent/EP0408338B1/de not_active Expired - Lifetime
- 1990-07-11 EP EP90307585A patent/EP0408340B1/de not_active Expired - Lifetime
- 1990-07-11 DE DE69022650T patent/DE69022650T2/de not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4400548A (en) * | 1981-08-17 | 1983-08-23 | Union Carbide Corporation | Hydroformylation process using bisphosphine monooxide ligands |
US4748261A (en) * | 1985-09-05 | 1988-05-31 | Union Carbide Corporation | Bis-phosphite compounds |
US4904808A (en) * | 1986-06-13 | 1990-02-27 | Eastman Kodak Company | Chelate ligands for low pressure hydroformylation catalyst and process employing same |
Cited By (19)
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US5324850A (en) * | 1989-08-23 | 1994-06-28 | Societe Nationale Elf Aquitaine | Preparation of chiral catalysts based on ruthenium and phosphorus complexes |
US5430191A (en) * | 1992-01-31 | 1995-07-04 | Hoffmann-La Roche Inc. | Phosphorus compounds |
US5457219A (en) * | 1992-01-31 | 1995-10-10 | Hoffmann-La Roche Inc. | Phosphorus compounds |
US5508438A (en) * | 1992-01-31 | 1996-04-16 | Hoffmann-La Roche Inc. | Phosphorus compounds |
US5530162A (en) * | 1992-04-13 | 1996-06-25 | Research Corporation Technologies, Inc. | Process for the hydrogenation of aryl phosphines and products obtained therefrom |
US5306834A (en) * | 1992-07-16 | 1994-04-26 | Takasago International Corporation | Process for preparing optically active 4-methyl-2-oxetanone |
US5412109A (en) * | 1992-07-16 | 1995-05-02 | Takasago International Corporation | Process for preparing optically active 4-methyl-2-oxetanone |
US5808162A (en) * | 1995-07-21 | 1998-09-15 | Takasago International Corporation | Chiral unsymmetric diphosphine compound and transition metal complex containing the same as ligand |
US20030093387A1 (en) * | 2000-06-09 | 2003-05-15 | Brett Nakfoor | Electronic ticketing system and method |
US20050021365A1 (en) * | 2000-06-09 | 2005-01-27 | Nakfoor Brett A. | Multi-input access device and method of using the same |
US20050021364A1 (en) * | 2000-06-09 | 2005-01-27 | Nakfoor Brett A. | Method and system for access verification within a venue |
US20050021450A1 (en) * | 2000-06-09 | 2005-01-27 | Nakfoor Brett A. | Electronic ticketing system and method |
US20060095344A1 (en) * | 2000-06-09 | 2006-05-04 | Nakfoor Brett A | System and method for fan lifecycle management |
US8131572B2 (en) * | 2000-06-09 | 2012-03-06 | Flash Seats, Llc | Electronic ticketing system and method |
US8346580B2 (en) | 2000-06-09 | 2013-01-01 | Flash Seats, Llc | System and method for managing transfer of ownership rights to access to a venue and allowing access to the venue to patron with the ownership right |
US9697650B2 (en) | 2000-06-09 | 2017-07-04 | Flash Seats, Llc | Method and system for access verification within a venue |
WO2007082026A2 (en) * | 2006-01-10 | 2007-07-19 | The Trustees Of Boston College | Catalytic enantioselective silylations of substrates |
WO2007082026A3 (en) * | 2006-01-10 | 2007-11-22 | Trustees Boston College | Catalytic enantioselective silylations of substrates |
US20090312559A1 (en) * | 2006-01-10 | 2009-12-17 | Hoveyda Amir H | Catalytic enantioselective silylations of substrates |
Also Published As
Publication number | Publication date |
---|---|
EP0408338A2 (de) | 1991-01-16 |
JPH03275691A (ja) | 1991-12-06 |
EP0408340A2 (de) | 1991-01-16 |
DE69025003D1 (de) | 1996-03-07 |
DE69022650T2 (de) | 1996-05-02 |
DE69022650D1 (de) | 1995-11-02 |
EP0408340B1 (de) | 1996-01-24 |
EP0408338A3 (en) | 1991-06-19 |
EP0408340A3 (en) | 1991-07-03 |
JPH0692427B2 (ja) | 1994-11-16 |
EP0408338B1 (de) | 1995-09-27 |
US5087728A (en) | 1992-02-11 |
DE69025003T2 (de) | 1996-09-12 |
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